CN104611699B - Preparation method of magnesium alloy surface micro-arc oxidation-electrophoresis composite coating - Google Patents

Preparation method of magnesium alloy surface micro-arc oxidation-electrophoresis composite coating Download PDF

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CN104611699B
CN104611699B CN201310536595.8A CN201310536595A CN104611699B CN 104611699 B CN104611699 B CN 104611699B CN 201310536595 A CN201310536595 A CN 201310536595A CN 104611699 B CN104611699 B CN 104611699B
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magnesium alloy
electrophoresis
arc oxidation
preparation
composite coating
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CN104611699A (en
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常立民
田利丰
刘伟
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Harbin specification Technology Co.,Ltd.
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Jilin Normal University
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Abstract

The invention discloses a preparation method of a magnesium alloy surface micro-arc oxidation-electrophoresis composite coating, and belongs to the field of magnesium alloy surface treatment. The preparation method is used for solving problems of conventional magnesium alloy that biological activity is poor, and bonding force with composite membrane is low. According to the preparation method, micro-arc oxidation is adopted so as to form a micro-arc oxidized ceramic coating on magnesium alloy surface, and a composite coating with biological activity is obtained via electrophoresis treatment using a pulsed power supply; and a used electrophoretic liquid is composed of one compound selected from hydroxyapatite, acetic acid, and absolute ethyl alcohol or polyethylene glycol, and one compound selected from lanthanum nitrate or cerous nitrate. Ideal combination of micro-arc oxidation with pulse electrophoresis is realized; compounds such as hydroxyapatite are introduced onto the surface of magnesium alloy; and electrophoresis treatment is used for hole sealing of holes of the micro-arc oxidized ceramic coating so as to improve biological activity and corrosion resistance of magnesium alloy, and bonding strength is relatively high.

Description

A kind of preparation method of magnesium alloy surface micro-arc oxidation-electrophoresis composite coating
Technical field
The present invention relates to the preparation method of alloy surface differential arc oxidization-electrophoresis composite coating, thus prepared compound painting Layer has good corrosion-proof wear performance, it is expected to become a kind of novel biomedical material.
Background technology
Magnesium and magnesium alloy base biomaterial are most possibly to become Metal Substrate body implanting material of future generation.Magnesium metal it is close The Young's moduluss of degree and magnesium are close to people's bone, can avoid stress-shielding effect；The internal indispensable element of magnesium behaviour, content is only Inferior to calcium, sodium and potassium, while magnesium is also the main component for constituting bone, bone, tooth and cell can be promoted to be formed, and in the ore deposit of bone Important adjustment effect is played in substance metabolism.Even if generating magnesium ion in human body fluid, also can be absorbed by surrounding body tissues Or excreted by metabolism, with biodegradability.Therefore, magnesium and its alloy have considerable as biomaterial Application prospect.The differential arc oxidization technique for growing up on the basis of anodic oxidation in recent years can be used for the modified place in surface of magnesium alloy Reason, is a kind of up-and-coming Mg alloy surface the features such as its generated in-situ porous oxide coatings has nontoxic, anti-corrosion, wear-resisting Treatment technology.Differential arc oxidization technique has following prominent characteristics：The matrix phase transformation caused using conventional high-temperature coating can be avoided And embrittlement；Realization forms uniform ceramic deposit in complex-shaped or porous surface metallic substrate surface；Oxide layer and base Body set is firmly, easy to control to aoxidize composition of layer, thickness；Equipment is simple and convenient to operate；Film layer preparation cost is low；Technique green ring Protect.Hydroxyapatite molecular formula is Ca10(PO4)6(OH)2, it is osseous tissue and the main inorganic composition in tooth.Human body dentin Middle hydroxyapatite accounts for 70%, and 90% is accounted in enamel, and enamel surface accounts for more than 95%.Hydroxyapatite has excellent Biocompatibility, biological activity and bone conductibility, from the point of view of the physical arrangement of hydroxyapatite, it is believed that bone is a kind of bullet The hydroxyapatite based composites of property high molecular polymer toughness reinforcing.The composition of artificial-synthetic hydroxyapatite, structure and human body The inanimate matter constituent structure of osseous tissue is similar, it have it is nontoxic, nonirritant, without sensitization, without mutagenicity and carcinogenecity, A kind of biocompatible materialses, can with ostosis chemical action, with good bone conductibility.Electrochemical deposition has equipment Simply, low cost, the advantages of easy to operate, depositing operation is easy to control.But in electrochemical deposition process, electrolyte temperature, base The condition such as bottom and electrolyte composition all can produce impact to the composition of electrochemical deposition calcium phosphorus product, structure and surface topography etc., Therefore can also there are problems that hydroxyapatite coating layer is low with metal surface bond strength.
The content of the invention
It is an object of the invention to overcome the shortcoming of above-mentioned prior art, the method for carrying out electrophoretic process using the pulse power Differential arc oxidation-the electrophoresis of high-quality is formed in magnesium alloy differential arc oxidation sample surfaces（MgO/HA）Composite coating.
The preparation method of the magnesium alloy surface micro-arc oxidation/electrophoresis composite coating of the present invention is concretely comprised the following steps：
First, the preparation of magnesium alloy surface micro-arc oxidation film layer：Pretreated magnesium alloy will be carried out and be placed in work in electrolyte For anode, corrosion resistant plate carries out differential arc oxidation and processes 3-20min as negative electrode, obtains the magnesium alloy with differential arc oxidation film layer It is standby；
（1）The preparation method of wherein described electrolyte is as follows：Weigh raw material sodium aluminate or potassium aluminate 15-50g/l, hydroxide Sodium or potassium hydroxide highly basic 1-10g/l, hydrogen peroxide or potassium permanganate or potassium fluoride 1-10g/l, glycerol 1-10ml/l, lactic acid Sodium 5-30ml/l, dissolves in successively in deionized water, obtains electrolyte described in step one；
（2）The wherein treatment process condition of differential arc oxidation：With magnesium alloy product as anode, the insoluble inert metal of rustless steel It is negative electrode in above-mentioned electrolyte, negative and positive interpolar applies the pulse power carries out differential arc oxidation process, and technological parameter is：Voltage： 300-500V, temperature：5-50 DEG C, the time：3-20min, pH value：8-14；
Preprocessing process refers to and raw material magnesium alloy is polished successively using 400,1200,2000 mesh sand paper in the step one After polishing, the ultrasonic cleaning of at least one of deionized water, acetone or alcohol etc. is processed and completed.
2nd, the preparation of magnesium alloy differential arc oxidation-electrophoresis composite coating：To there is differential arc oxidation film layer obtained in step one Magnesium alloy is placed in electrophoresis suspensioning liquid as negative electrode, the insoluble inert metal of rustless steel be anode, two die openings 1cm, in electrophoresis In suspension, constant pressure electrophoretic process 100-500s is carried out using the pulse power, reaction takes out magnesium alloy 80 ~ 100 after terminating It is dried at DEG C, obtains the magnesium alloy with differential arc oxidation-electrophoresis composite coating；
（1）The preparation method of wherein described electrophoresis suspensioning liquid is as follows：Weigh hydroxyapatite respectively first（HA）5-50g/ L, dehydrated alcohol 10-200ml/l or Polyethylene Glycol 5-50ml/l, Lanthanum (III) nitrate or cerous nitrate rare-earth cation 1-10g/l, it is molten successively In deionized water, and with second acid for adjusting pH value to 2 ~ 6,1 ~ 3h of supersound process is then carried out, finally stir 12 ~ 24h, walked Electrophoresis suspensioning liquid described in rapid two；
（2）Ability cathode electrophoresis process process conditions be：With Jing differential arc oxidations process magnesium alloy sample as negative electrode, stereotype or The insoluble inert metal of rustless steel is anode, and two die openings 1cm in above-mentioned electrophoresis suspensioning liquid, using the pulse power perseverance are carried out Pressure electrophoretic process, technological parameter is：Voltage：50-300V, positive dutycycle：20-60%, negative sense dutycycle：10-40%, frequency： 50-500Hz, temperature：5-50 DEG C, the time：100-500s, pH value：2-6.
The advantages of the present invention are：
1st, adding in the electrolyte of the inventive method step one after glycerol or sodium lactate can suppress arc discharge, reduce The aperture of ceramic membrane surface, improves the corrosion resistance of film layer；The electrophoretic process of step 2 can process what is obtained in step one Differential arc oxidation sample surfaces obtain the thin layer containing hydroxyapatite and calcium and P elements, make sample have certain biology living Property；Add after cerium ion in the electrophoresis suspensioning liquid of step 2, improve the calcium-phosphorus ratio of the composite film after processing, further improve The biological activity of composite film；The Mg alloy surface of the electrophoretic process of step 2 has loose structure, and adopts the pulse power Electrophoretic process is carried out, the bond strength that figure layer is combined after processing is improve.Therefore, obtained after differential arc oxidation and electrophoretic process Composite coating there is certain biological activity, corrosion resistance is good, and high with substrate combinating strength.
2nd, the method for the present invention has obtained the compound figure layer with corrosion resistance and certain biological activity in Mg alloy surface, thick Degree can reach 10-40 μm.Jing after differential arc oxidation process obtains porous ceramic film, hydroxyl is added in ceramic membrane using electrophoretic process The calcium phosphorous compounds such as base apatite, make sample have certain biological activity.
3rd, the present invention obtains the composite coating with inside and outside double-layer structure using the electrophoretic process process conditions of optimization, its Inner compact layer is complete, is the composite oxides of Mg, Al, and combines closely with parent metal；Its outer layer is smooth, is hydroxyapatite And the composite oxides containing Ca, P, with biological activity.
Description of the drawings
Fig. 1 is the electron scanning micrograph of the differential arc oxidation film layer that the present invention is obtained in Mg alloy surface；
Fig. 2 is the electron scanning micrograph of differential arc oxidation of the present invention-electrophoresis composite coating；
Fig. 3 is the elementary composition energy spectrum analysiss of differential arc oxidation of the present invention-electrophoresis composite coating；
Fig. 4 is the XRD crystal species analysis of differential arc oxidation of the present invention-electrophoresis composite coating, and abscissa is 2 θ, and vertical coordinate is strong Degree.
Specific embodiment
Embodiment one：
First, the preparation of electrolyte：Weigh raw material sodium aluminate or potassium aluminate 20g/l, sodium hydroxide or potassium hydroxide 3g/l, mistake Hydrogen oxide 2ml/l, glycerol 3ml/l, sodium lactate 5ml/l, dissolve in successively in deionized water, obtain electrolyte standby.
2nd, the preparation of electrophoresis suspensioning liquid：Weigh hydroxyapatite respectively first（HA）10g/l, Polyethylene Glycol 10ml/l, nitre Sour cerium 2g/l, is dissolved in deionized water successively, and with second acid for adjusting pH value to 4, then carries out supersound process 2h, finally stirs 24h, obtains electrophoresis suspensioning liquid standby.
3rd, the preparation of magnesium alloy surface micro-arc oxidation film layer：Pretreatment will be carried out（The preprocessing process is referred to and closes in magnesium After golden raw material is using 400,1200,2000 mesh sand paper successively sanding and polishing, at least one of deionized water, acetone or alcohol etc. Ultrasonic cleaning is processed and completed）Magnesium alloy be placed in electrolyte as anode, corrosion resistant plate as negative electrode, carry out differential arc oxidation 3 ~ 20min, obtains the magnesium alloy sample with differential arc oxidation film layer；Electrolyte temperature is controlled for 5 ~ 20 DEG C, micro-arc oxidation process is joined Number is：Electric current density is 200mA/cm2, frequency is 100Hz, positive dutycycle 35%, negative sense dutycycle 35%, final voltage 450V；As shown in Figure 1, the film layer that the present invention is obtained in Mg alloy surface is typical differential arc oxidation pattern.
4th, the magnesium alloy sample of step 3 process is placed in electrophoresis suspensioning liquid insoluble lazy as negative electrode, rustless steel etc. Property metal be anode, two die openings 1cm in electrophoresis suspensioning liquid, using the pulse power constant pressure electrophoretic process 200s carry out, and react Magnesium alloy is taken out after end is dried at 90 DEG C, complete the preparation method of magnesium alloy surface micro-arc oxidation-electrophoresis composite coating, The technological parameter of electrophoretic process is：Voltage density is 40V/cm2, frequency 100Hz, positive dutycycle 45%, negative sense dutycycle 30%.
The electron scanning micrograph of the differential arc oxidation that Fig. 2 present invention is obtained-electrophoresis composite coating, as shown in Figure 2, this The magnesium alloy differential arc oxidation of invention-electrophoresis composite coating surface distributed is uniform, the typical differential arc oxidation pattern after electrophoretic process Disappear, the more uniform electrophoresis film shape of distribution is presented.
Fig. 3 is the elementary composition energy spectrum analysiss of differential arc oxidation-electrophoresis composite coating that the present invention is obtained, and following table is for wherein The mass percent and atomic ratio of calcium, phosphorus and oxygen element：
The elementary composition EDAX results of differential arc oxidation-electrophoresis composite coating that table 1 is obtained for the present invention
Element Wt% At%
O 43.40 63.31
P 21.88 16.48
Ca 34.71 20.21
Ca/P 1.59 1.23
From Fig. 3 and Biao 1, calcium and P elements are introduced in the Mg alloy surface after electrophoretic process, its calcium-phosphorus ratio The calcium-phosphorus ratio 1.67 of close hydroxyapatite.It can be seen that, the differential arc oxidation-electrophoresis composite coating prepared by the present invention has certain Biological activity.
Fig. 4 is the XRD crystal species analysis of differential arc oxidation-electrophoresis composite coating that the present invention is obtained, and abscissa is 2 θ, indulges and sits It is designated as intensity.As shown in Figure 4, the Mg alloy surface after electrophoresis introduces the hydroxyapatite with biological activity.
Table 2 is directly to carry out electrophoresis in Mg alloy surface（HA/Mg）, using D.C. regulated power supply in magnesium alloy differential arc oxidation Sample surfaces electrophoresis（AC-HA-MAO/Mg）The differential arc oxidation obtained with the present invention-electrophoresis composite coating（PC-HA-MAO/Mg）'s Bond strength is contrasted：
HA/Mg AC-HA-MAO/Mg PC-HA-MAO/Mg
σ 6.32MPa 10.35MPa 13.56MPa
Wherein σ is the resisting binding strength between coating and matrix.
As shown in Table 2, the adhesion for carrying out the composite coating that electrophoresis is obtained on magnesium alloy differential arc oxidation film layer surface is obvious Higher than directly in the sample of Mg alloy surface electrophoresis, and electrophoretic process is carried out with micro-arc oxidation films layer surface, using pulse electricity Source carries out the adhesion of the sample of electrophoresis compared with being significantly increased using D.C. regulated power supply.
Embodiment two：
Present embodiment and electrolyte in step one unlike embodiment one by concentration for 3g/l potassium hydroxide, The sodium aluminate of the hydrogen peroxide of 2ml/l, the glycerol of 3ml/l, the sodium lactate of 8ml/l and 20g/l is made.Other steps and technique Parameter is identical with embodiment one.
Embodiment three：
Present embodiment is from electrolyte in step one unlike specific embodiment one by the hydroxide that concentration is 3g/l The sodium aluminate of potassium, the hydrogen peroxide of 2ml/l, the glycerol of 2ml/l, the sodium lactate of 4.5ml/l and 25g/l is made.Other steps And technological parameter is identical with embodiment one.
Embodiment four：
Present embodiment is from micro-arc oxidation process parameter in step 3 unlike embodiment one, two or three：Electric current Density is 200mA/cm2, frequency is 100Hz, positive dutycycle 35%, negative sense dutycycle 35%, final voltage 400V.Other steps And technological parameter is identical with embodiment one.
Embodiment five：
Electrophoresis suspensioning liquid is 5g/l by concentration in step 2 unlike one of present embodiment and embodiment one to four Hydroxyapatite, the cerous nitrate of 2g/l and the Polyethylene Glycol of 10ml/l make.Other steps and technological parameter and embodiment One is identical.
Embodiment six：
Electrophoresis suspensioning liquid unlike one of present embodiment and embodiment one to five by concentration for 10g/l hydroxyl phosphorus The Polyethylene Glycol of lime stone, the cerous nitrate of 5g/l and 10ml/l is made.Other steps and technological parameter are identical with embodiment one.
Embodiment seven：
In step 2 unlike one of present embodiment and embodiment one to six electrophoresis suspensioning liquid by 10g/ hydroxyl Apatite, the cerous nitrate of 2g/l and 50% dehydrated alcohol composition, solvent is water.Other steps and technological parameter and embodiment One is identical.
Embodiment eight：
The technological parameter of electrophoretic process is electricity in step 4 unlike one of present embodiment and embodiment one to seven Percent consolidation is 35V/cm2, frequency 100Hz, positive dutycycle 45%, negative sense dutycycle 30%.Other steps and technological parameter and reality Apply mode one identical.
Embodiment nine：
The time of electrophoretic process is 250s in step 4 unlike one of present embodiment and embodiment one to eight.Its His step and technological parameter are identical with embodiment one.
Embodiment ten：
The time of electrophoretic process is 300s in step 4 unlike one of present embodiment and embodiment one to eight.Its His step and technological parameter are identical with embodiment one.

Claims (5)

1. the preparation method of a kind of magnesium alloy surface micro-arc oxidation-electrophoresis composite coating, it is characterised in that：
(1) magnesium alloy differential arc oxidation is processed：
A () differential arc oxidation processes the preparation method of electrolyte：
Weigh raw material sodium aluminate or potassium aluminate 15-50g/l, sodium hydroxide or potassium hydroxide 1-10g/l, hydrogen peroxide or permanganic acid Potassium or potassium fluoride 1-10g/l, glycerol 1-10ml/l, sodium lactate 5-30ml/l, dissolve in successively in deionized water, are electrolysed Liquid；
(b) differential arc oxidation process process conditions be：
Voltage：300-500V, temperature：5-50 DEG C, the time：3-20min, pH value：8-14；
(2) pulse electrophoresis of the magnesium alloy with differential arc oxidation coating are processed：
The preparation method of the electrophoresis suspensioning liquid of (a) pulse electrophoresis process：
Weigh hydroxyapatite (HA) 5-50g/l, dehydrated alcohol 10-200ml/l or Polyethylene Glycol 5-50ml/l, nitre respectively first Sour lanthanum or cerous nitrate are 1-10g/l, are dissolved in deionized water successively, and with second acid for adjusting pH value 2~6, then carry out ultrasound 1~ 3h, finally stirs 12~24h, obtains electrophoresis suspensioning liquid；
(b) pulse electrophoresis process process conditions be：
Voltage：50-300V, positive dutycycle：20-60%, negative sense dutycycle：10-40%, frequency：50-500Hz, temperature：5- 50 DEG C, the time：50-500s, pH value：2-6.
2. according to the magnesium alloy surface micro-arc oxidation described in right 1-electrophoresis preparation method of composite coating, it is characterised in that carry out micro- Sodium lactate, glycerol are added during arc oxidation processes, the corrosion resistance of magnesium alloy sample is improve.
3. according to the magnesium alloy surface micro-arc oxidation described in right 1-electrophoresis preparation method of composite coating, it is characterised in that the arteries and veins Power supply that electrophoretic process adopts is rushed for the bidirectional, dc pulse power.
4. according to the magnesium alloy surface micro-arc oxidation described in right 1-electrophoresis preparation method of composite coating, it is characterised in that the arteries and veins It is that, with magnesium alloy differential arc oxidation sample as negative electrode, stereotype or rustless steel are anode, in hydroxyapatite suspensions to rush electrophoretic process In, negative and positive interpolar applies pulse carries out electrophoretic process.
5. according to the magnesium alloy surface micro-arc oxidation described in right 1-electrophoresis preparation method of composite coating, it is characterised in that utilize arteries and veins Rushing power supply carries out electrophoresis, improves the corrosion resistance and bond strength of magnesium alloy surface micro-arc oxidation-electrophoresis composite coating.
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